DE2004983C3 - Silver halide color photographic emulsion - Google Patents

Description

CH ₂ C-NHCO ^>

contains.

6. Silver halide emulsion according to claim 1, characterized in that it is a magenta coupler Compound of formula

H ₃ CO

N = N-CH C-NHCO

contains.

The [farbpholographische invention relates to a silver halide Kmulsion, as a magenta coupler I-phenyl · pyr, which is enthüll i / () lon ⁽¹ J) is substituted in position {a residue having a Siiccininiidogmppe.

From de. "US l'iitenlschrifl i \ ^hl> l2 Miigcniakuppler for farbphotogiapliisehe silver Lniulsionen are already known, which consist of a l-l'henyl-pyra / olon-C"), the one in position over { These well-known gastric lacticulators have the disadvantage that they are not sufficiently soluble in the commonly used coupler solution and have the tendency to turn the idea of the oil into a l In addition, in the Kenel they are only very difficult to obtain under the use of less accessible and expensive basic materials. They also have the disadvantage that the first Color images have been prepared using color photographic silver halide emulsions which reveal these magenta couplers, are relatively unstable to light, heat and humidity, and none e have sufficient absorption properties in the desired wavelength range.

Krfindiing is therefore based on the task improved magenta coupler for use in a color photographic silver halide I .miilsii ι η indicate that are easily soluble in the commonly used coupler solvents and not for Aiiskrisiallisierung tend and with their help it is possible IN THE. l'arbphologiaphisclie silver halide I niiilsioncri to manufacture the larbhilder with an improved

Provide light, warmth and ability to shine.

The invention relates to a color photography Silver halide emulsion, the "l.s Miigenuikuppler a 1-Phcnyl-pyr «/ olon- (5) reveals, which in 3-position || ung substituted via a residue with a succinimido lip which is characterized by tin!) of the miigenii coupler corresponds to the formula

Z- -CH /
N
I. c— O C.
^y \ \ N /

CO-CH-R

CO — CH,

wherein

R for an alkyl group with 8-18 carbon atoms

or an alkynyl group,
A for -NHCO- or -NH-.
X stands for a halogen atom or a methyl, alkoxy,

Aryloxy or alkoxycarbonyl group,
η for an integer from 1 to 3.
Y stands for hydrogen or a halogen atom.
Z is hydrogen or an arylazo group

and the succinimido stem on the nucleus is in 3- or 4 position.

That in the color photographic silver halide emulsion Magnetic couplers used in the invention. which are so-called proprietary couplers acts, have the following advantageous compared to the previously known, comparable magenta couplers Characteristics:

1. Sr are in high boiling solvents, such as Dibutylphthalal, Tricrexylphosphat and the like., Easily soluble, so that for the dissolution of the coupler required amount of solvent can be reduced, whereby it is possible. one to cool a highly concentrated and stable dispersion;

2. They do not crystallize out of the emulsions or the coated and dried films:

3. The holographic silver halide emulsions prepared using such magnetic couplers provide color images with excellent spectral absorption characteristics. the opposite Light, heat and moisture have a high resistance;

4. In addition, the gastric couplers used according to the invention can be activated by a simple ring closure reaction with splitting off of water from an alkali-soluble coupler of the synthetic monoamide type. which has diffusion preventing groups easily on an industrial scale getting produced.

It is believed that the above-mentioned excellent properties of the present invention used magnetic couplers for long-cell alkyl sucrinimide grips, which come in 3 or 4 positions on a l'henylkern are bound, are attributable.

The '~ in the farhphotographischcn Silberhiilogcnid emulsion of the invention entha ¹ NEN Magenlakuppler can be prepared as indicated below:

A! - (substituted phenyl-3-benzamido or • Aminoanilino) -5-pyroazolon is used with a long Alkyl succinic anhydride condenses, forming a succinic acid monoamide compound (hereinafter referred to as the non-ring-closed coupler). This not ring-closed cnc Coupler is then heated with a sulfuric acid / acetic acid mixture, and the Ring closure then takes place with elimination of water. The product obtained is under Purified using suitable processes, with the desired coupler reverberating in high purity will.

The long-term alkyl succinic acid anhydride. Which which represent the main starting products are, for example, in "Dai-Yukikiigaku (Grand Organic Chemistry)". Volume 4, ropes 366. published by Asakura Sholen. Tokyo. It refers to Compounds that are produced on an industrial scale using malonic acid ester !! and long-celled Alkyl halides can be produced. In detail, the foundations can be used Gastric couplers can be prepared in the manner described in the following synthesis examples:

Synthcscbcispicl I

A mixture of 39.8 g of 1- (2,4,6-trichlorophynyl) -3- (3-amidobenzamido) -5-pyrazolone and 400 ml of glacial acetic acid is stirred and crosslinked with 35.2 g of octadceyl succinic anhydride. The mixture is heated to 80 ° C. for one hour. 40 ml of concentrated sulfuric acid are then added admitted. After the mixture has been left to stand at the mentioned temperature for 10 minutes. it is poured into 2 l of water, whereupon a white precipitate appears. This is done by filtering removed, washed with water, dried and timkrislallisiert from 200 ml of ethyl acetate. One obtains 50 g of a white powder (yield 68.5%) which is the compound 1 (2,4,6-trichlorophynyl) -3- (3-ocladecylsuccinimidobenzamidoJ-S-pyrazolone of the formula (I) given below. The after used according to the invention indicated below Gastric couplers (2) to (14) are produced.

CH ₂ C -NHCO

Il C N

c / N

ci I ci

N <

CO-CH-C ₁₈ H,

\ ι

CO - CH ₂

(F. 162 - 163 C)

Cl

(2) 1- (2,4,6-Trichlorophenyl) -3- (4-octadecylsuccinimido-anilino) -5-pyrazolone.

_ CO-CH-C ₁₈ H, -

C- H ₂ C- - NH - / ';> - N ζ

C- _N "'CO-CH ₂

O N

ci; ci

(F. 78 - 82 "C)

Cl
(3) 1- (2.4.6-Trichlorophynyl) -3- (2-chloro-4-octadecylsuccinimido-anilino) -5-pyrazolone

\ CO-CH-C ₁₈ H ₃₇

CH ₂ C-NH ^ / -n /

_{c N} ⁼ 'CO-CH ₂

O N

ci; ci

, (F. 90 - 92 C)

Cl
1- (2- (chlorophenyli-3- (4-octadecenylsuccinimido-anilino) -5-pyrazolone

_ CO-CH-C ₁₈ H, -

CH ₂ C-Nf

C N

O N

Cl

_y - N <

CO - CH,

(F. 86 ^C ~ 90 ⁰ Q (5) 1 - (2,4,6-TrichloφhenyI) -3- (3-octadecenyIsucciniπlido-benzaInido) -5-pyΓazolon

CO - CH - (CH ₂ ) ^ CH =

CH ₂ C - NHCO- ^ a

C N

f \ /
ON

Cl : Cl

! i;

CO - CH ₂

(F. 148 ^C - 150 ⁰ C)

9 10

(6) 1- (2,4,6-Tiichloiphi'nyl) -3- (3-octadecenylsuci; imido-bon / aiTiido) -5-pyrazolone

CH ₂ C-NHCO-v

Il ^ -

C N

Cl! Cl

Cl

CO - CH - CH - CH (CH ₂ I ₁₅ CH.,

N _n

CO - CH ₂

(F. 78 - 80 C)

(7) 1- (2,4,6-Trichlorophenyl) -3- (3-dodecylsuccinimido-benzamido) -5-pyrazolone CH, -C NHCO \ ^>

ι 'Il - <

^C \ / ^N ~ N <

CO-CH ₂

CO --- C ¹ HC ₁₂ H ₂ ,

O N

egg! egg

(F. 158 - 159 C)

Cl

(8) 1 - (2,4,6-Trichlorophenyl) -3- {3-octylsucciniinido-benzamido) -5-pyrazolone

CO-CH-C ₈ H ₁

(9) 1- (2,4-Dimethyl-6-chlorophynyl) -3- <3-octadecylsuccinimido-benzamido) -5-pyazolone CH ₂ C — NHCO-

I Il

C N

O N

α I CH,

CO-CH-C ₁₈ H ₃₇ CO-CH ₂

(F. 73 ° - 74 ° C)

CH ₃

(10) 1 - {2,4-Dimethyl-6-ch ^ oφhenyl) -3- <2-chloro-5-octadecy ^ succπliπlido-benzaInido) -5-pyΓazolon

Cl

CH ₂ C-NHCO

I Il

C N

O N

α ^ cn,

CO-CH-C ₁₈ H ₃₇ CO-CH ₂ (m.p.! 03 ° ~! 05 ⁰ Q

CH,

ti

(II) 1- (2-Chl (irphenyl) -3- (3-octadecyisuccinimido-benzamido) -5-pyrazolone

CH ₂ C-NHCO

I 11

C N

O N

Cl

CO-CH-C ₁₈ H ₁₇

CO-CH ₂

(F. 147 - 150 C)

(12) 1- (4-Methoxyphenyl) -3- (3-dodecylsuccinimido-benzamido) -5-pyrazok) ii

CH ₂ C-NHCO

1 ti

I I!

C N

ON CO-CH ₂

(I J (F. IKO - 181 C)

OCH,

(13) 1- [4- (4-t-Butylphenoxy) phenyl] -3- (3-diidecylsici: imido-benzamido) -5-pyrazolone

CH ₂ C-NHCO

C N

O N

CO-CH-C ₁₂ H

N <

I2 "25

CO-CH ₂

(F. 174 "- 176 C)

IC ₄ H ₉

(14) 1 - (4-Ethoxycarbonylphenyl) -3- (4-octadecylsuccinimido-benzamido) -5-pyrazolone

CH ₂ C - NHCO - C> - N <

ι ^z Il X = / \

CO-CH-C ₁₈ H ₃

C N

O N

CO-CH ₂

(F. 732 ° ~ 225 ° Q

COOC ₂ H ₃

Synthesis example 2

3.6 g of p-anisidine is mixed with a mixture of 40 ml of water, 10 ml of concentrated hydrochloric acid and 2.4 g> Sodium nitrite diazotized. To the obtained diazonium SaI /. 80 ml of alcohol are given.

A solution of 14.6 g of the above coupler (4) in 146 ml of pyridine is added at 5- 10 ⁰ C to the above-described solution of the diazonium salt, in

After stirring for 3 hours, the mixed solution is diluted with 350 ml of water and then mixed with 150 ml of concentrated hydrochloric acid, with a Precipitation is deposited. This is collected by filtration, washed with water, dried and recrystallized from alcohol, whereby 13 g of an orange-red powder with the melting point 187-189 ° C can be obtained in a yield of 75.6%. This coupler is mentioned below Link.

(15) i- ^ 2,4,6-Trichloφhenyl) -3- (3-octadecylsuccinimido-benzamido) -4- (4-methoxyphenylazo) -5-pyrazolone

H ₃ CO

CO CH

CO - CH ₂

For the production of light-sensitive silver halide color photographic emulsions by _{comparison! N} application of the above couplers can all conventional methods are used. For example, one, two or more of these couplers in a high-boiling solvent with a boiling point above 175 ° C, such as tricresyl phosphate or dibutylphtha- ^ lat, or in a low-boiling solvent such as butyl acetate or butyl propionate, or, if necessary, in a mixture of these two Solvent are dissolved, and the solution is then mixed with an aqueous gelatin solution containing a surfactant. The mixed solution is then emulsified using a high-speed rotary mixer or a colloid mill. The emulsion obtained is then immediately added to a photographic silver halide emulsion and coated on a suitable support, such as a film support or baryta paper. It is then dried in order to remove most of the low-boiling solvent. Alternatively, the emulsion described above can be solidified and then extruded into a noodle shape which is then washed with water or subjected to similar treatments to remove the low boiling solvent. Then these noodles are added to photographic emulsions. The resulting overall emulsion is coated on the above-mentioned support, followed by drying. A photographic light-sensitive material can be prepared in the manner described above.

The couplers used according to the invention can be used together with a non-ring-closed one Couplers are used, and a proportion of 5-30% of a non-ring-closed coupler affects the The dispersibility of the coupler is favorable and has the effect that separation of the coupler is prevented.

The amount of coupler added to a photographic silver halide emulsion is preferably in the range of 10 to 100 g per mole of silver halide. However, it is not always limited to this area.

example 1

20 g of the coupler (5) to be completely dissolved at 8O ⁰ C in a mixture of 20 ml of dibutyl phthalate and 60 ml of butyl acetate. This solution was admixed with 10 ml of a 10% strength aqueous solution of Alkenol B (alkylnaphthalene sulfonate, manufactured by Du Pon * Co.) and 200 ml of a 5% strength aqueous gelatin solution. The mixed solution was then treated in a colloid mill to prepare a coupler dispersion. This dispersion was added to 1000 ml of a highly sensitive gelatin-silver iodobromide emulsion, which was then coated on a film support. It was then dried to obtain a stable photosensitive photographic film. The light-sensitive photographic film obtained in this way was exposed in the usual way and then ^{treated at 20 °} C. for 10 minutes with a developer solution of the following composition:

Ν, Ν-diethyl-p-phenylenediamine-

hydrochloride 2 $ g

Anhydrous sodium sulfite 2.0 g

Sodium carbonate (monohydrate) 82.0 g

Potassium bromide 2.0 g

Water up to 1000 ml

The film developed in this way was subjected to the usual stop and fixative treatments, watered for 10-15 minutes, and then with a for 5 minutes Treated bleach solution of the following composition:

Kalhamferricyanide 100 g Potassium bromide 50g Water except for 1000 ml

The film was then soaked for an additional 5 minutes and for 5 minutes with a fixing solution of the the following composition fixed:

Sodium thiosuIiUt (pentahydrate) 250 g Water up to 1000 ml

Then the recording material became 20-25 Watered for minutes and then dried, a brilliant magenta color image with an absorption maximum of 532 πιμ was obtained.

Example 2

10 g of Coupler (6) was added at 60 ⁰ C in a mixture au "10 ml of tricresyl phosphate and 30 ml of butyl acetate fully dissolved this solution was ml with 5 of a 10% aqueous AJkanol B solution and 20OmI of a 5% aqueous solution of gelatin mixed. The mixed solution was treated in a colloid mill to prepare a dispersion. The dispersion was added to 500 ml of a gelatin-silver iodobromide emulsion, which was then coated on a film support and dried to obtain a photographic light-sensitive material. The material obtained in this way was exposed and then developed for 10 minutes at 20 ^° C. with a developer solution of the following composition:

Metol 3.0 g Sodium sulfite anhydrous 60.0 g Hydroquinone 6.0 g Sodium carbonate anhydrous 50.0 g Potassium bromide 1.0 g Water except for 1000 ml

The recording material thus developed was subjected to the usual stopping and film hardening treatments, washed and then subjected to a second exposure to white light. Development was then carried out for 12 minutes at 20 ^° C. with a developer solution of the following composition:

N.N-diethyl-p-phenylenediamine 5.0 g Anhydrous sodium sulfite 2.0 g Sodium carbonate (monohydrate) 82.0 g Potassium bromide 1.0 g Water up to 1000 ml

45

The material was then stopped in the usual way, fixed, watered, bleached and then 20 Watered for minutes. Finally it was dried, leaving a positive magenta color image of high Clarity with an absorption maximum at 530 πιμ was obtained.

50

55

Example 3

10 g of Coupler (9) were completely dissolved at 50 ⁰ C in 20 ml Dibütylphthalat. This solution was mixed with 5 ml of a 10% strength aqueous alkananol B solution and 200 ml of a 5% strength aqueous gelatin solution mixed The obtained mixed solution was then treated several times in a colloid mill to prepare a dispersion. This dispersion was added to 500 ml of a gelatin-silver chlorobromide emulsion, which was then applied to a baryta paper and dried to prepare a photosensitive recording material. The lichtemp-sensitive material thus prepared was exposed to 10 minutes lanj developed at 20 ⁰ C in a bath of the following composition:

N-ethyl-N-hydroxyethyl

p-phenylenediamine sulfate 2J5 g

Anhydrous sodium sulfite 2.0 g Hydroxylamine hydrochloride 1.0 g Sodium carbonate (monohydrate) 82.0 g Potassium bromide 2.0 g Water up to 1000 ml

The material thus obtained was immersed in a stopper containing 10 ml of glacial acetic acid, 3 g of caustic soda and 1000 ml of water minutes ir a bath of the following composition bleached at 2O ⁰ C:

EDJA · 2 Na (disodium salt of Ethylenediaminetetraacetic acid) 40.0 g Ferric chloride 30.0 g Sodium carbonate (monohydrate) 20.0 g Potassium bromide 30.0 g Sodium thiosulfate (pentahydrate) 200.0 g Water up to 1000 ml

35 The material so treated was soaked for 20 minutes, then in a stabilizing bac for 2 minutes immersed and dried with a magenta color image with an absorption maximum at 535 πιμ which was excellent in light fastness.

Example 4

6.0 g of the coupler (5) and 2.0 g of the coupler (15 'were in a mixture of 8.0 ml of dibutylphthalai and 24 ml of butyl acetate completely dissolved at 80 ° C. These Solution was with 4 ml of a 10% strength aqueous alkanol B solution and 80 ml of a 5% strength aqueous solution Gelatin solution was added, and the mixed solution was processed into a dispersion Dispersion was added to 400 g of a highly sensitive silver iodobromide emulsion, which was then added! a film support was applied and dried, urr to manufacture a photosensitive photographic recording material.

The light-sensitive so prepared photographic material was by conventional methods exposed unc then treated in the same manner as in Example I beschrieber to give a yellow positive image τημ with an absorption maximum at 435, and a magenta color image was obtained with an absorption maximum at 540 m \.

809 840/12!

Claims (5)

Patent claims: I. Color photographic silver halide emulsion, which is a l-phenyl-pyrazolone (5) as a magenta coupler contains that in 3-position over a remainder with a succinimido group is substituted thereby indicated that the magenta coupler conforms to the formula Z-CH C— A - <\> ι Ii \ = x I Il j. CN ^Γ CO - CH - R
CO - CH ₁ (X) _n R stands for an alkyl group with 8-18 carbon atoms or an alkenyl group. A for -NHCO- or -NH-. X for a halogen atom or a methyl, alkoxy, aryloxy or alkoxycarbonyl group, η for an integer from I to 3, Y for hydrogen or a halogen atom, Z for hydrogen or an arylazo group and the sicciniinide residue on the phenyl nucleus is in 3 or 4 position. 2. Silver halide emulsion according to claim 1, characterized in that it is a Magcnta coupler Compound of formula CO-CH-C ₁₈ H CH ₂ lS ^rl J7 CO-CH ₂ O N ci I ci Cl cnlhäll. 3. Silver halide emulsion according to claim I, characterized in that it is a Miigenla-Ktipplcr Compound of formula CH ₂ C-NHCO-A I Il C N O N Cl I (Ί CO-CH (CH ₂ ) _H CH CH (CH ₂ I ₇ CH, CO CH, Cl cnlhäll 3 4. silver hulogenide emulsion according to claim I, characterized in that it is a magenta coupler Compound of formula CH ₁ C-NHCO contains. 5. Silver halide emulsion according to claim 1, characterized in that it is a magenta coupler Compound of formula